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Quantum Electronic Atomic Rearrangement by H2 Recombination Energy Release and Solid State Material Low Energy Nuclear Reaction

by Stephane NEUVILLE TCE consultant, F-77165 Cuisy +33 (0)6 4147 1922 Email: stephane.neuville709@orange.fr

During exothermic physical and chemical recombination, it has to be considered that electronic activation occurs before heat will be released. Quantum electronic activation is achieved when electrons are excited up to higher electronic energy bands. Those can then often induce specific atomic rearrangement in competition to usual thermodynamic thermal atomic rearrangement ruled by Arrhenius law. This has been evidenced with carbon material showing higher diamond-like properties when exposed to different type of activation. Quantum electronic activation criteria involving steric conditions and optoelectronic band gap of the final state have been worked out. An effect which could be demonstrated in more details after revision of some fundamentals of hard carbon Raman characterizing we review. Among important effects, the H2 and N2 chemical recombination energy release (CRER) when not counterbalanced by heat degradation phenomena transforming the material towards its graphite thermodynamic ground state. Several unexpected demonstrative examples we also review are confirming the effect and which is also concerning some other types of material. Considering that atomic rearrangement can modify the electronic environment of interstitial H2, some influence on some corresponding solid state LENR will be expected. Revisiting some nuclear quantum physics fundamentals, the Lawson fusion criterion could be reformulated in terms of wave-packet superposition and impact energy. Considering further on the Mossbauer Effect, we suggest that the modified geometric distribution of electronic orbitals will consequently also modify the distribution of the nucleus wall potential in favor of some easier tunneling and higher LENR efficiency. This effect is expected to be combined and cumulated with other type of fusion by inertial confinement involving impact of energetic H+ ions on dense carbon material, leading to some convenient new design of carbon/ hydrogen LENR fusion plasma reactor, which is expected to have high COP.

Highlights: Atomic rearrangement of solid state materials. Graphitic and Diamond-like carbon. Carbon material characterizing with differentiated Raman spectroscopy. Plasma-surface interaction. Application to solid-state nuclear reaction.

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I. INTRODUCTION. Hydrogen incorporated in metals and solid state materials is known to significantly change their physical and chemical properties. Because hydrogen is monovalent, important bonding chain discontinuities can appear. If chemically bonded on one side (M-H…), then the considered Hydrogen atom will be only weakly bonded on other side. Instead of strong M-M-M chains, it will be possible to have weak M..H-H..M chains considering the high bonding energy of H-H (~5eV) (same for O-H) in comparison to C-H (~ 4 up to 4.5 eV) and other M-H binding energy which can be much lower [1]. However, with such binding energies H can be absorbed to quite high amount at room temperature in more or less porous and less dense metals, but which can also be easily broken and recombined to H2 at higher temperature and released by exodiffusion. Weak Van der Waals and hydrogen bonds explain the plastic properties of many polymers, when low cohesion of adjacent monomer and polymeric chains is provided. Concerning last mentioned materials, the discontinuities of interatomic binding energy also explain their relatively reduced thermal and chemical stability and their reduced hardness. This can be observed with a-C:H materials with various hydrogen content in comparison to other hydrogen free hard diamond like carbon material containing also high amount of sp3 [2]. Frozen methane containing 100% sp3 has nothing to do with diamond and has like frozen water only relative low hardness (hardness ~ density of cohesion energy). All this explains why H can produce exodiffusion of H2 and marked H+ channeling effects in ordered crystalline materials at relatively reduced temperature in many metals and less dense materials [1]. H can also be more tightly trapped in denser and harder materials such as ta-C:H and glassy carbon, last one in spite being porous, which has also good diffusion-barrier properties for Hydrogen [3-4] similar to graphene sheet, ta-C and ta-C:H [5]. However, trapped H can nevertheless recombine to H2 chemical when the temperature is high enough with energy recombination energy release (CRER). This is generally not only producing additional heat, but also inducing anomal atomic rearrangement [6]. These effects, we discuss next, are not always explained as usually expected with thermal thermodynamics of interatomic bonds and density of enthalpy. Produced phase mixture for which each phase can have different specific structure and density of cohesion energy is then not only ruled by the Arhenius law, as described with usual metallurgy physics [7]. Many experiments concerning chemical synthesis and formation of metastable material have shown, that quantum electronic activation effects obtained for instance with various photonic excitation can have some decisive role for the achievement of some desired specific molecular configuration, and what is not possible to do in replacing photon activation by equivalent heat introduced from outside [8]. Higher activation energy level and rates is able to produce atomic rearrangement towards harder and denser diamond like carbon structure for instance [2, 6]. This is also the case for other type of materials presenting different state of material structure, for instance

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when amorphous hydrogenated Si is rearranged to microcrystalline Si by intense higher photon energy laser light irradiation or with intense hydrogen plasma-surface interaction [9] and what can then also occasionally transform the texture of metallic alloys and affect their mechanical properties [1]. In such cases, the structure of the material being modified and the atomic density being enhanced, many other properties may also change especially when those have semiconducting properties (mechanical, optical, electric optoelectronic, electrochemical, thermal and chemical stability etc.) [5-6]. Corrolary: the electronic environment of substitutional or interstitial molecular and atomic species will then also be changed. Considering that protons are involved in many nuclear fusion processes, quantum electronic atomic rearrangement in solid state material achieved with hydrogen recombination is expected to have also some influence on Low Energy Nuclear Reaction (LENR) [10]. In order to contribute to the clarification of this aspect, we revisit some nuclear physics fundamentals with which we suggest some reformulated Lawson law of nuclear fusion for condensed matter [11]. This is leading us to discuss some feasibility of a carbon reactor, using the Bethe- Weizsäcker CNO nuclear fusion cycle [12]. For this achievement, several aspects have to be sorted out first:

The quantum electronic atomic arrangement of material is best shown with carbon material because presenting one of the most marked differences between solid material structure and properties (GLC Graphite-Like Carbon and DLC Diamond-Like Carbon). However, considering the numerous states between monocrystalline diamond and monocrystalline graphite, many atomic rearrangements will concern these intermediary states. Therefore, the effect can only be clearly evidenced here with some accurate characterization of the different carbon types in their complex numerous different structures which often are simultaneously associated [5-6, 13-15]. Raman spectrometry has been considered for this purpose to be one of the best suited characterizing techniques. However, many confusing incoherent aspects could be found in the literature, which have been only recently sorted out and corrected [14]. The updated correct assignement of many Raman peaks will be necessary for the discussion on quantum electronic atomic rearrangement. Therefore, we will first briefly review in §II the corresponding Raman revised state of the art before discussing the subject of atomic rearrangement in §III. We will then suggest in § IV some extention of fundamentals concerning the dual wave-paquet/particle representation, and especially concerning atom nucleus mass, electric charge and wall potential barrier distribution with which the Lawson fusion criterion can be adapted to solid state LENR. II. BRIEF REVIEW ON UP-DATED CARBON RAMAN SPECTROMETRY. II.1. Carbon structures to be considered with RAMAN spectroscopy Different types of carbon materials including micro and nano-crystalline diamond, amorphous diamond, ta-C, degraded ta-C, ta-C:H, composite diamond-like carbon with inclusion of sp3 cluster, sp2 cluster and stacks of sp2), a-C:H, a-C (amorphous homogeneous mixture of sp3 and sp2), composite graphite-like carbon, glassy carbon (porous mix of fullerenic,DLC and GLC), amorphous graphite, single/multiwall SWCNT/

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MWCNT, Wire CNW, Fiber CNF, multilayer /singlelayer graphene, fullerenic and graphenic particles, micro/nano polycrystalline graphite which have been reviewed in detail elsewhere [5]. Observing here, that most non-crystalline carbon materials will not correspond to the general term of amorphous carbon (which does not contain any ordered substructures such as sp3 or sp2 clusters).

In such a case the difficulty to correctly assign each band and each peak is often linked to insufficient consideration brought to peak and band broadening, band overlapping and band shift. Notwithstanding that very often some possible atomic rearrangement has not been considered (for instance when unexpected D diamond peak appears in a carbon Raman sprectrum, which cannot be explained without anomalous atomic rearrangement, as can be observed with some glassy carbon material for instance [16]. Therefore, we will first review with followings, some up dated carbon Raman spectrometry fundamentals, which will be necessary to be considered for the detailed description of atomic rearrangement phenomena. Before looking at Raman spectra structure, different general characterizing features have to be checked. In case of carbon material [2, 5-6] it must be checked ratio of sp2:sp3 (for instance with carbon Auger peaks, which appears to be one of best method), hardness (~density of cohesion energy), stress (recall relation between stress and Raman shift with Pauleau formula briefly discuss next), hydrogen content, contamination, thermal stability and elaboration process conditions defining which effect induces which atomic rerangement (precursor material, temperature, impinging particles energy and flux, dissociation, ionization,) and which have been reviewed and discussed in more details in [2, 5-6]. Much confusion in Raman peak assignement has been resulting from misfit on theoric quantum mechanic and general fundamentals [14-17] whenever having decisely contributed to scientific progress in these domains. This concerns for instance the double resonance Raman scattering, atomic disorder, amorphous state, band broadening, compressive/tensile stress Raman peak up-/downshift and especially concerning the so-called Ddisorder peak at ~1350cm-1 [18-21] which is all the more confusing it is closed to the rhombohedral D diamond peak at ~1330cm-1 and the hexagonal chair structure H6 diamond peak at ~1325 cm-1 [22-23].

Carbon materials achieved with different thin film deposition devices correspond often to composite material which may contain nearly all sorts of different kinds of substructures [2, 5-6, 13-15] (summarized with Fig.1) and which properties strongly depend on their distribution, size and structure, and on how they are interlinked to each other. More accurate structure assignment analysis will help describing atomic rearrangement.

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Confusion also exist on so-called G Band [20] originaly only assigned to Csp2-Csp2 bonds and which in reality corresponds to overlapping of different Raman broaden peaks corresponding mainly to odd rings C5/C7 (~1520/1550 cm-1) [14, 24], hexagonal ring structure of graphenic materials(~1580cm-1) corresponding to stationary phonon mode within such ring) [14, 22], olefin Csp2-Csp3 (~ 1490/1510 cm-1) [25] and olefin Csp2-Csp2 (~1620 cm-1) which can also be observed with IR spectroscopy [26]. Another origin of increased confusion could often be found when same designation D is still currently used for different carbon material types and different effects: diamond and disordered (amorphous) diamond [27-28], D graphene (so-called Ddisorder peak [18], DLC disorder [20-21] (atomic disorder , amorphous state, mix of sp2 and sp3, crystalline defects, isotopes, impurities, interstitials, vacancies, dangling bonds etc.). In addition when so-called D’, D” designation have been used, which are corresponding to other substructures and to other resonance effects than currently described [14, 29]. This is the reason why we have proposed with ref.[14] also a new Raman nomenclature which will give more differntiated account for main observed carbon Raman peaks and band with Fig.7 (end of §II) after general discussion on carbon Raman spectroscopy II.2. Comparison between Raman spectra of different Carbon material types Raman results obtained with different types of carbon material can show paradoxical quite similar Raman spectrum, especially concerning the « D » band and the « G »band but which can be in reality distinguished with band broaderning effects and stress shift. Raman spectra in Fig.2 of a)ta-C, b) micro-diamond, c) glassy carbon and d) a-C:H [19, , 22, 28,31] have here to be compared respectively with those in Fig.3 of a’) pseudo amorphous graphite containing also sp3 and similar amorphous graphite (GAC) and, b’) crystalline/amorphous diamond, c’) carbon nanofiber, and d’) modified glassy carbon [26, 32-35]. It has been shown since longer time that the so-called general D band is not always to be assigned to concentration of sp3 in carbon material For DLC material containing some significant amount of sp2 it is shown that the ID/IG ratio (corresponding to integrated intensity of D and G band ) is in fact proportional to the density of graphitic crystallites for some intermediaty range of their size [17]. Those appears during annealing of crystalline diamond above ~ 800/900°C [25] and grow with annealing temperature and time since graphite is known to correspond to the thermodynamic carbon ground state. No « D » band is observed in large grain polycristalline graphite and crystalline graphite particles [22, 25], meanwhile it is observed for small graphite dust particles [36]. It will then be necessary to know what the so-called Ddisorder peak in reality is in looking about Raman spectrometry fundamentals in more details.

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Fig.2. Raman spectra of a) ta-C, b) Nano-diamond, c) Glassy carbon and d) a-C:H

Fig.3. Raman spectra of a’) amorphous graphite, b’) a- diamond, c’) C NanoFiber, d’) modified glassy carbon

Ta-C by Anders et al [19] As grown (60GPa, 80%sp3) ~ 40cm-1stress upshift.Csp2-Csp3 and C5/C7 band ~ 1620/1660cm-1. Annealed at 500°C no stress shift (40GPa, 60% sp3). Csp2-Csp2 ~1620cm-1

Nano-diamond by Mc Namara et al [28] diamond peak superimposed on amorphous diamond band and disordered G band and so-called D disorder band

Glassy carbon by Huong et al [22].Gpeak. 10cm-1 upshifted G and D diamond peak. So-called disorder (GedgeA) at~1360cm-1 in coherence with socalled 2D peak at ~2720cm-1

a-C:H annealing by Wagner et al [31] disordered diamond appears at ~1330cm-1, tensile stress reduced (H2exodiffusion) G peak getting sharp. Graphite crystallites grow in sp3 matrix.

Amorphous “diamond like” Ion irradiated glassycarbon Prawer et al [32] upshift15cm-1.sp2-sp3. Or (shifted similar spectrum shape) Evaporated amorphous graphite tensile stress downshift 10cm-1 Rouzaud et al [33] .sp2-sp2.

D diamond by Huong et al ref.[27]~1330cm-1 Ordered crystalline diamond (sharp peak), amorphous diamond (symmetric broad pic). No sp2. No graphene edge (Ddisorder) 1350cm-1

CNF by Y.Y.Lin et al ref. [34] G+1580cm-1

, G- 1560cm-1 (CNT intern walls), no GeA, no sp2-sp3, H6 (hexagonal chair diamond 1325cm-1 , (sp2 rearranged in sp3 of outer CNT wall. during process

Raman spectra glassy carbon N+ irradiated by Iwaki et al [35] ~ 40cm-1 stress upshift GeA~1390cm-1, G~1610cm-1, disorder sp3diamond~1370cm-1 sp3-sp2band (DG)~1510cm-1 Similar to annealed a-C:H

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II.3.General Aspects of Raman Fundamentals.

II.3.1. Classical and quantum mechanical description of Raman scattering. Raman theory basing on classical description are reviewed in many published works [37] and has been refined with quantum mechanical aspects involving photon/electron/phono scattering and with which ordered crystalline structures such as diamond, graphene, CNT could be better characterized [18, 20-21]. Specific phonon modes in ordered crystalline material exist according to their wavevector direction and can be described with phonon dispersion curves in the reciprocal space, and what has been determined also for diamond [23] and for graphene [38] (Fig.4).

For infinite ordered crystalline material, some simplified quantum mechanical theory predicts that phonon is supposed to correspond to a delocalized representation of interatomic vibration mode. However, several aspects will contradict this assumption. Beside progressing wave which can be backscattered on structure edges, interferences and stationary waves have also to be considered; notwithstanding that local phonon exist in free molecules [37] and that material disorder will affect the interatomic force constant (distribution of constant forces) with which phonon modes can be modified [39].

II.3.2. Role of stress and atomic disorder on Raman shift and band broadening In real more complex and disordered structure, [39] the number of phonon modes is much higher. However, considering some duality between quantum mechanical representation and classical vibration mechanics, the atomic vibration modes which are ruling the Raman effect can be qualitatively described with some simple anharmonic oscillator composed by two atoms of same mass in considering the interatomic energy potential U = α.x6 and the resulting force constant K= 2α.x-4 [40]. Considering that the Force constant K is shifted

Fig.4. Phonon dispersion curves of graphene based on interatomic constant force by Lazzeri et al [38]

G peak at 1580cm-1 corresponds to double degeneracence

in-plane phonon mode on Γ point (stationary vibration mode within hexagonal Csp2-Csp2 cyclic ring). So-called Ddisorder peak at ~1350cm-1 corresponds to a double degeneracence in-plane phonon mode on near K point (Coupled Double Resonance scattering sequence on a symmetric A edge Csp2-Csp2 bond (extern edge of graphene sheet or intern edge of voids in graphene)

So-called 2D peak at ~2700cm-1 corresponds to addition of D disorder phonon (2K mode on A edge), and in the bulk to 2K and 2M phonon modes Raman active (single M phonon mode at ~1350cm-1 is not Raman active)

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by ∆K by internal stress Ϭ, the phonon frequency will be shifted by δω/ω0

= Ϭ(1-ν)/E0

(Pauleau formula) [40] (ν Poisson coefficient, E0 mean elastic constant) showing that

* Raman shift is proprotional to internal stress. In amorphous (disordered) material interatomic distance is xi= x0+δxi (δx distortion) and considering the interatomic energy potential U = α.x6, the strain δx

i distribution

corresponds also to phonon frequency shift δωi distribution with δω

i /ω

0 = η. δx/x

0 [14].

Therefore, *Band broadening associated to atomic disorder II.3.3. Locality of scattering event and confinement effect. Raman anomalies have been generally considered to be the consequence of some “confinement” (of phonon and electrons) due to modification of interatomic binding energies on edges and in smaller particles by the modification of their electronic orbital environment. [30, 42-45], However, experimental results are not always in accordance with such predicted effects. Further on local phonon vibration mode has been evidenced with microRaman on graphene A edges corresponding to so-called D disorder peak (~1350cm-1) [46-47]. Fig.5

Fig.5. Micro Raman experimental results showing graphene ZZ edge transformation into Aedge with annealing at ~300°C adapted from Xu et al [47]. No C5/C7 band at~1490/1530cm-1. Tensile stress downshift ~15 cm-1 on pristine material. Dpeak at 1350cm-1 localized on external Aedge. D signal spots in bulk corresponding to internal A edge of voids. D’ peak is reduced with annealing temperature at~300°C

This can also be deducted from the graphene phonon dispersion curves in the reciprocal space [18, 30, 38, 45] for the G Raman peak corresponding to the Γ point at 1580cm-1 and which corresponds to some stationary phonon vibration mode within the hexagonal cyclic sp2 ring. Recall that the direction of the wavevector in the reciprocal space corresponds to a propagation wave direction in the real space. However, on the Γ point of these curves the phonon wavevector direction is perpendicular to the graphene plane for which no phonon wave propagation perpendicular to the plane can here exist. Similar consideration exists also for electronic orbital locality of valence band electron in hexagonal cyclic sp2 rings, when modified by some magnetic field and determining some Hall effect.[48-49].

Confinement effect in smaller sp2 clusters based on Quantum Mechanical calculation appears often to be overestimated, when predicted results on Raman shifts [43] can be also interpreted with other more likely effects [14]. For instance when considering what can happen during annealing of a-C:H [31]. As grown a-C:H can be differently stressed depending on which process has been used . It can have tensile stress when significant H2 and CHx exodiffusion is produced during its growth, and with a reduced ion implantation.

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Compressive stress then appears in consequence of growth of sp2 clusters which have lower atomic density than their surrounding amorphous diamond-like material. When enough H2 recombination is available, then some more ordered diamond-like material can be produced in the sp2 surrounding matrix. Continuing the annealing process, compressive stress will be relaxed.

Overestimated electronic confinement effect can also be documented with the calculation of the optoelectronic gap of small sp2 clusters [42], which is much higher than experimentally measured.

II.3.4. Double resonance theory and phonon backscattering on edges and defects.

The developed double resonance (DR) theory basing on successive Raman scattering events in sp2 clusters and graphene flakes is considering that beside the fulfilment of the energy conservation law also the law of impulse conservation law has to be fulfilled [43]. Last one is achieved in considering some phonon backscattering on edges and defects [18, 30]. Looking at existing phonon modes at ~1350 cm-1 it appears that the so-called Ddisorder Raman effect can be interpreted in terms of phonon backscattering on Atype (symmetric Armchair) graphene edges. This is in agreement with what is observed with Micro Raman analysis [46-47](Fig.5), and also with the point that the corresponding Raman signal is not observed for larger graphite crystallite when it is smaller than the signal noise background of bulk material Raman light [14].

The traditional quantum mechanic formalism, considering that phonon are delocalized, interprets the backscattering process in term of “intra valley” and “inter valley” scattering events [18, 30, 45] corresponding to adjacent Brilloin zones. However, looking with more care to the energy balance, it appears that this model is not respecting the law of energy conservation. Therefore, we have worked out another model (Couple Double Resonance theory) [14] providing fullfilment of energy conservation law basing on classical/quantum mechanic dual representation of electron and phonons. We consider the locality of involved photon, electron and phonon and that backscattered phonon can be either absorbed by activated electron or by corresponding hole, the important difference of scattering time of interacting photon, electron and phonon and the activated electron/hole energy and proximity. This model will not be discussed in more details here.

However, it gives account for many observed particularities. Coupling and resonance between different phonon modes and overtone modes within a same hexagonal cyclic sp2 ring explains the dependence of Raman signal with different orientation of polarized laser light, and how the corresponding Raman signal can be local [14]. This model clearly shows then that the so-called Ddisorder Raman peak is always appearing on symmetric Aedge (Armchair shape edge). It is not appearing on graphene related materials such as hexagonal BoronNitrogen material (hBN) [50] for which the Aedge is not corresponding to a symmetric oscillator. The so-called Ddisorder peak is sharp when corresponding phon at 1350cm-1 is backscattered onsymmetric Aedges of well ordered material, and appears in form of broad band when the material is disordered. However, such backscattering can

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also exist within the surface bulk of graphene and CNT. In fact, it corresponds then to backscattering on internal edges of vacancies and voids [14] in agreement to experimental observation on CNT [51-52].

The model gives also account for the so-called D’ peak at ~ 1620cm-1 (supposed to be the result of confinement effect and intervalley scattering process). In fact, it shows that this D’ peak corresponds to dangling Csp2-Csp2 bonds on graphenic materiel extern and intern edges of voids and which can also be evidenced with IR spectroscopy [26].

Fig.6 summarize this interpretation, especially in showing that Ar+ ion bombardment of a graphene sheet is first creating vacancies and voids, for which the D and D’ peaks are staying sharp and what documents the well ordered structure of these edges. Band broadening appears for all peaks including the G peak when the ion impact zones are overlapping with higher ion doses and the hexagonal cyclic sp2 rings destroyed [55].

Considering all kind of confusion about designation and assignement of Raman peaks and bands which have often appeared in published papers about carbon material investigation during last decades, we have proposed some new Raman nomenclature of main peaks and band observed during carbon engineering [14] for which we reproduce it with table.1.

Fig.6 a) Raman spectra of cut exfoliated graphene: no disorder in the bulk (sharp G peak) and Coupled Double Resonance CDR at ~1350cm-1 on A edge by Cançado et al [53]

b) Csp2-Csp2 bonds (D’~1620cm-1) on cut graphene edge. Double dangling edge bonds: addition of D’ phonon to 2D’ (3240cm-1)(Similar effect on internal edge of voids created by Ar+ irradiation

c) Raman spectra of Ar+ ion irradiated graphene by Dresselhaus et al [55]. D peak corresponds in fact to internal Aedges of voids). Atomic disorder only appears with higher ion doses (broad bands)

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III. REVIEW ON ATOMIC REARRANGEMENT EFFECTS III.1. Graphitic thermal degradation and metastable diamond-like material reforming. Considering that graphite is the ground state of carbon, any carbon material can be degraded towards more graphitic material by thermal effects, and what is known to correspond to Arrhenius law applicable to metallurgy and solid state physical chemistry [7-8, 30, 43]. This effect is generally observed during thermal annealing of diamond [22, 25, 56] and with what is finally achieved after longer thermal annealing of different kinds of DLC and a-C:H [20, 31] and with annealing of different volumic carbon material such as filled carbon wires and fibers [34, 57]. Some materials such as hollow carbon nano tubes (CNT), or graphene which are materials close to the graphitic ground state (containing same hexagonal cyclic rings like in graphite) will not be degraded anymore and can have some of their defects healed to some extend, until arriving to their sublimation temperatures (~ 3500°K) [29, 58].

It is known that diamond, which is a metastable material, is formed when higher temperature is associated to pressure and that its thermal graphitic degradation starts at about 800°Cwhen no other physical and chemical effects will hamper this process [56]. This is the reason why diamond-like materials have been considered to be achievable with

Table 1.Revised main Carbon peaks and band Raman No menclature

Raman cm-1

Peak/Band Type of structure binding Energy in ev

~ 1330 Ddiamond peak Ordered Diamond cubic Csp3-Csp3 at~7.02 eV

~ 1325 DH peak Ordered H6 Hexagonal Diamond Chair structure of hexagon Csp3-Csp3 ~ 7.015 eV

~ 1220/ 1400 Ddiamond band Disordered/amorphous Diamond Csp3-Csp3~ 7.02 +/- 0.01 eV

~ 1150 De1 Boundaries and edges of diamond crystallite

Aliphatic Csp3-Csp3

~ 1470 De2 Interface diamond/sp2 matrix Aliphatic Csp3-Csp2

~ 1580 G peak Graphene in plane cyclic ring Stationary vibration mode

Csp2-Csp2 ~ 7.03 eV

~ 1550/1650 ~ 1620 ~ 1540

G band Ge1 Ge2

GAC (Amorphous graphite) Adjacent C-C bond on hexagonal cyclic ring edges

Csp2-Csp2 ~ 7.03 +/- 0.01eV Dangling Csp2-Csp2 Dangling Csp2-Csp3

~ 1490 ~ 1540

G C5 G C7

C5 odd ring sp2 C7 odd ring sp2

Upshifted to ~1550 cm-1

on bended plane of fullerene

~ 1350 GeA A edge of graphenic material (former so-called disorder peak)

Coupled double resonance Raman. 0° backscattering

~ 1300/1400 GeA band Disordered A edge Random shift by edge defect

~ 2700 G 2P Two phonon double resonance Always seen together with GeA

Addition of two K or two M phonon

~ 150 ~ 1560 ~ 1600

RBM G- G+

Breathing mode of CNT Distorse G mode longitudinal Distorse G mode transversal

Radius dependent Helicoidal (semiconducting) Bended plane compression

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some thermal spikes during plasma and ionic processes [20]. However, many other effects different from pressure and thermal spikes have been identified favorizing the achievement of diamond-like materials and diamond (Hot filament diamond deposition, and low bias plasma deposition [56], the influence of energetic UV (> 5 eV) [58], the influence of X ray irradiation [59] and especially where atomic H is recombined to H2 [60] independently from external input of heat). It is observed in Filtered Vacuum Arc devices depositing ta-C, the role of ion flux (independently from the heating effect) releasing neutralization energy and the role of ion implantation producing compressive stress in favor of DLC with higher sp3 content, an effect which can then also be put in comparison with Diamond process making use of heat and pressure [61, 62].

With updated Raman spectroscopy can be shown in many published work that carbon material processing supposed to produce definitively graphitic material, are in fact containing some DLC and nanocrystal diamonds. This is shown for instense with graphitic material which is simultaneously heated up to 3000°K and irradiated with energetic intense UV [63] and with the achievement of glassy carbon corresponding to graphenic and fullerenic material containing sp3 and which is somewhat diamond like (hardness ~15 GPa) and for which a D diamond peak is observed at ~1330cm-1 indicating the existence of diamond nano-crystallites [22, 64] (meanwhile only a reduced Ddisorder peak at ~1350cm-1 corresponding to GeA edge phonon modes is observed).

III.2. Role of an electric field on diamond-like rearrangement of graphitic materials. Several experiments have shown how an electric field can produce diamond like atomic rearrangement of more graphitic materials [65]. An electric field is known to produce molecule distortion and polarization, which can then initiate atomic rearrangements, when the polarizing energy Ep is higher than the threshold energy at which a structure can be transformed into another one. This concerns particularly the rearrangement of hexagonal cyclic sp2 ring which can be transformed in a chair structure, an effect which is observed in applying an electric field on aromatic coumpounds [66]. Considering stack of hexagonal cyclic sp2 ring in multilayer graphene, in graphite and in multiwall carbon nano tube, those can be transformed into stack of chair shape hexagonal cyclic ring which are known to be in a sp3 hybridization state [22, 23](Fig.7) (the H6 diamond structure) This is an effect which is suggested to correspond to some intermediary step of graphite being transformed into diamond with combined heat and pressure (whenever in such a case this transformation is produced without electric field).

Fig.7. Stack of chair shape hexagonal cyclic ring corresponding to H6 diamond structure with sp3 and Raman frequency at ~ 1325 cm-1 according to Spear et al [23]

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It is nevertheless to consider how an electric field can be produced in a growing carbon material film, with the different reported activation mechanisms which are in favor of DLC material growth. This can be achieved with UV and X ray irradiation, although heat will also be produced which is in favor of some graphitic degradation.

However, we could show in former published work, how adsorption of molecules on some semiconducting material is producing a transient transverse electric field, similar to what is achieved with the Dember effect [67]. This is achieved when electron holes having different diffusion mobilities are activated in a semiconducting thin film (before producing heat). But for which could be shown that this electronic activation is not the consequence of an increased temperature, but via a direct transfer of the adsorbtion energy to the valence band electrons. Published investigation on CO molecule adsorbtion on a Ni substrate is confirming this effect in evidencing IR photon emission corresponding to the same adsorbtion energy release, without producing heat on the substrate [68].

III.3.Role of released chemical recombination energy on valence band electron excitation. It is then to be emphasized, that released neutralization energy (~10 eV), chemical recombination (~1 up to ~20eV) and adsorption energy (~7 eV in case of C-C on appropriate site) produce quite high activation energy considering the high adsorbtion energy of carbon atom on an appropriate site where it can be bonded to another carbon (~ 7 eV). Last one which can be combined with other kind of chemical recombination energy release (CRER) such as H-H [~5eV] and N-N [~12eV] (other type of CRER can be considered with O-H, F-H etc.). Experimental results have shown the importance of H CRER [56, 60], whenever the actual final energy release has to be considered (Fig.8) Table 2 giving a list of possible recombination energy release.

Fig.8. Difference of Glassy Carbon Hardness depending on polymer precursor

a) Low Hydrogen CRER Activation b)High Hydrogen CRER Activation

Disordered monomer configuration lower density of CRER. => less sp3

Ordered monomer configuration higher density of CRER => more sp3 and higher hardness

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Particular remarquable results have been achieved with N CRER during 700°C annealing of N rich CNx (with mainly atomic substitution Nitrogen)[15] and Fig.9.

III.4. Critrium of quantum electronic sp3 activation. Carbon material can be assimilated to semiconducting material, although some species such as graphite and metallic nanotubes have overlapping electronic valence σ/π and conduction σ*/π* bands. Fig.10 shows the calculated band structure of different carbon material type by Beeman et al [69].

Table 2.Chemical Recombination Energy Release in hard carbon deposition Hot Filament, PACVD and flame diamond a-C:H deposition

Fig.9. Clearance on possible diamond crystal nucleation in annealed CNx

Formation of many diamond microcrystals observed in CNx containing high amount of atomic Nitrogen when annealed at temperature (~700°C), according to D.G. Liu et al [15].To be explained with sp3 activation theory. Controversial when annealing of CNx produces usually graphitic carbon because of molecular N2 content(few CRER)

H* + H* → H2 + (~ 5 eV) (F1) Chemical reactions in growing diamond and a-C:H Csp3-H + Csp3-H → Csp3 - Csp3 + H2 + (~ 3 eV) (F2) Csp3 -H + H* → Csp3 - Csp2 + H2 + (~ 0.5 eV) (F3) Csp3 < + 2 H* → Csp2 + 2H2 + (~ 1.5 eV) (F4) Csp3 < + 2 H* → Csp2 + 2H2 + (~ 1.5 eV) (F5) Csp2 < + Csp2 < → Csp2 - Csp2 + 2H2 + (~ 1 eV) (F6) Csp2 < + Csp3 < → Csp2 - Csp3 + 2H2 + (~ 1 eV) (F7) Csp3 < + Csp3 < → Csp3 - Csp3 + 2H2 + (~ 1 eV) (F8) (with C< representing CH2 ). To be added adsorbtion and neutralization energy release

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Considering that during an atomic rearrangement, the outer electron orbital activated electrons should always occupy authorized energy levels therefore we postulate that they should be activated to energy levels higher than both the original and the final state. For this achievement, several other conditions will have to be fulfilled. The number of activated electrons should be at least of same number than the number of atoms which are possibly rearranged. The activated atomic rearrangement is a five dimension phenomena involving local space, energy and time and for which simultaneity, activation energy level, activation intensity and decay of several activation event corresponding to number of activated valence band electron, which need to be compatible with the steric aspects. Some equation of atomic rearrangement have been established accordingly illustrating all aspects to consider [6, 14] we will not reproduce here in this review.

Fig.10. Density of electronic states in diamond, graphite, GLC , DLC and ta-C (0%sp2) According to Beeman et al [69]

Fig.11. Sp3 atomic rearrangement activation criteria

QUANTUM ELECTRONIC

REARRANGEMENT POSTULATE During atomic rearrangement, electrons of outer atomic shells, must always occupy authorized energy levels => valence electrons have to be excited up to conduction band levels of initial and final state before decay on final valence band level

1)Valence band electrons in graphite, GLC and DLC can be activated by thermal activation because of reduced opto-electronic gap and low energy transition π -> π*.

2)Whereas, for diamond and ta-C no significant π π* band exist (more or less only σ σ*bands) and gap > 3 eV has to be considered for which electron excitation needs a higher quantum electronic activation

3)Continuous band allows reduced thermal activation in favour graphitic degradation (with which Raman Effect appears with laser excitation at 514 nm (2,41 eV)< gap.

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Carbon material can have optoelectronic gap from very low value (in graphenic materials) with all intermediary values for DLC up to (~2.5/3.5 eV) for ta-C and up to ~5 eV for diamond. The rearrangement criterion applies also to carbon materials which will have lower final gap and for which corresponding lower activation energy level will be sufficient (subject that enough electron will be activated). To be observed the role of catalytic effects with which, the binding energy of C-H can be reduced and with which consequently the global CRER energy release will be higher, explaining thus , why addition of Boron in precursors of a diamond deposition process will produce better quality diamond as has been shown by Wang et al [70]

III.5. Influence of atomic rearrangements on disorder and stress. Atomic rearrangements are generally leading to the reduction of the internal stress [7, 16, 29, 59, 61] in consequence of reduction of defects. The reduction of the internal stress of carbon materials is often the consequence of exodiffusion of H2 and reduction of the number of included vacancies and interstitials with which higher final atomic packing density and better ordered material is achieved. This aspect is of particular importance to consider, when stress is much affecting carbon film adherence strength and stability [2, 5]. Stress in carbon material can be determined for instance in measuring mechanical bending of a thin substrate coated with the stressed material (reviewed in [2, 71]), or in measuring the Raman shift [41]. Considering that stress reduction is usually achieved with some thermal annealing, this way of doing will unfortunately in the same time generally degrade the carbon material to more graphitic less performing material. This is known for longer thermal annealing of a-C:H, a-C, ta-C and diamond at higher temperature which produces the growth of ordered sp2 clusters [17, 20, 31, 43]. However, it could be observed also that thermal treatment of some polymers and of some a-C:H, is not always immediately degrading the material to more graphitic material, and that the diamond-like character could be either much improved with the achievement of harder glassy carbon [3, 4, 16) or at least have the diamond character of a-C:H maintained for while [72]. However, stress can be reduced with carbon material restructuration with the application of an electric field, which is also enhancing its diamond-like character [65]. The reduction of stress is also observed when sp3 atomic rearrangement activation is produced meanwhile an annealing temperature was maintained without the material is degraded. This achieved for instance when using high photon energy (>5 eV) UV laser irradiation [59, 63]. This also appears with catalytic effects producing higher hardness and lower H content and which for instance can be achieved with Boron doping during a-C:H or diamond growth [ 6, 70]. It is also observed that diamond is generally produced at higher temperature, for which only graphitic soot would have been expected. Intense Hydrogen CRER in favor of sp3 activation, will compensate the thermal graphitic degradation with sp3 rearrangements and because of the achievement of some quite well ordered diamond structure, in general only thermal stress will be produced in consequence of different thermal dilatation coefficient between substrate material and diamond coating[56].

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III.6. Remarquable Examples of sp3 actomic rearrangement

Fig.12. Glassy carbon N+ irradiated transformed into ta-C by Iwaki et al [35]

Glassy carbon is transformed into compressive stressed (~30cm-1upshift) ta-C by combined N2 CRER, neutralization energy release. Decrease of Gpeak(~1610cm-1) with ion impact destruction of cyclic ring => decrease of GeA band originally at ~1350cm-1 stress upshifted to 1380cm-1 with ion peening. Increase of upshifted amorphous diamond band at~ 1360cm-1

Fig.13. Homogeny diamond film nucleation on Molydenum crystalline substrate

Two step carbon deposition by Ravi et al [73] a) Hot carbon non activated carbon deposition � disperse few surface carbon left after diffusion

b) C-C adsorption energy release activation only on few disperse spots (although added to H2 CRER � Discontinuous reduced Diamond nucleation

One step deposition by Hernberg et al [74] a) Homogeneous epitaxial carbon surface coverage not being absorbed by depth diffusion. b) Homogeneous dense C-C adsorption energy release activation + H2 CRER � Homegeny Diamond film nucleation

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IV. APPLICATION OF DIAMOND-LIKE REARRANGEMENT TO CONDENSED MATTER NUCLEAR FUSION. IV.1. Generality Considering that atomic rearrangement can form better ordered and denser material, compressive stress with specific local geometric distribution can be exerted on interstitial molecular material, which is all the more important the differences of initial and final density of cohesion energy is higher. This is suggested to be the case for atomic H incorporated by diffusion and ion implantation in less dense material before being rearranged in harder and denser ta-C materials by activation with Chemical Recombination Energy Release (CRER) and with which left atomic H and chemically recombined H2 can be trapped and placed in position to produce eventual nuclear reaction with other nucleus of neighbouring atoms. In harder ta-C over 80% of carbon atoms are in a sp3 hybridization state and the interatomic binding energy is about 7eV (nearly the same than in diamond where it is about 7.02 eV). In difference to diamond, ta-C has generally important compressive stress in the range of 500 to 1000MPa in consequence of the use of an ionic process producing ion peening. The ta-C atomic packing density is about 0.8 of the diamond packing density and about 1.5 higher than more graphitic a-C.This is representing compression energy per carbon atom in the 1 to 10 eV range, what appears as quite small in comparison to compression energy of about 1KeV to 10 KeV which is necessary to achieve nuclear fusion of free nucleus, (thermocuclear fusion with temperatures of about 10 million to 100 million °K). However, it is here to consider that 1 KeV to 10KeV corresponds to relatively common energy for different surface science equipments, and it will have primairily to be considered the flux of nucleous, the amount of nucleus to be incorporated in a solid state target, and how collision organized in a modified electronic orbital environment can be usefull for the achievement of more efficient condensed matter nuclear reactions. At this stage, it appears that it will not be the physical carbon material compression allone which will produce the nuclear reactions between neighbor atoms (including incorporated species) of the corresponding material and that different kind of chemical recombination energy release will have to be considered and which might be altering the measurement of eventual other type of energy release which origin might be nuclear for instance. Therefore, close attention must be brought to different effects which might be influencing the efficiency of Low energy nuclear reaction. This is particularly concerning the so-called Lawson criterion which defines the nuclear fusion collision condition [1]. For this achievement must be also reviewed some fundamentals, with which many results could be already achieved for the better knowledge of fusion nuclear physics [12]. IV.2. Revisting some nuclear particle physics fundamentals IV.2.1. Nucleus electrostatic barrier potential and atomic electronic orbital distribution. Fusion between colliding atom nucleus, is subject to the possibility to overpass their high Electrostatic barrier potential, which is supposed to have some spherical isotrope distribution and for which sufficient collison energy is necessary. This is explaining why

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independent nucleus will only produce fusion with higher collision energy whenever lower than originally predicted with more simplified theory, in consequence of some tunneling effect and for which colliding energy in the 1 to 10 KeV are necessary. However, it has to be taken the question if this electrostatic barrier can be modified in its isotrope distribution, thickness and amplitude, considering the existence of the Môsbauer effect which has been evidenced for many γ emitting isotopes (with unstable decaying nucleus) [75]. These experiments have shown that the emitted γ frequency is modified by many physical influences and especially by the electronic orbital environment of the considered nucleus. From this fact can be deducted that the quantum nucleus structure of these atom nuclei will also be modified by this electronic orbital environment. Looking at atoms which have been reported to be subject to nuclear fusion, it appears that beside atoms which have an isotrope spherical electronic environment (with 1s and 2s electronic shells- such as H, He, Li, Be), also atoms with 1p electronic shell have to be considered which have marked non isotrope electronic orbital-such as B atom with bilateral axial symmetry and for which is also to be considered some orbital hybridation, and degenaresence. The same orbitals can present here different spatial distribution and energy levels. The distribution of the electronic orbitals appears more complex for 3d electronic shell, and for which some of the atoms present also some ability to produce fusion. Several of them have catalytic properties and present some electronic degenarescence which makes possible some different distribution of their electronic orbitals with different chemical states, such as Ni and Cr. Their electronic orbital distribution appears then in agreement with the quantum mechanical calculation of the higher electronic energy levels of the hydrogen atom (represented in Fig.14).Ref.[76].

Considering that these distributions will be reflected on the quantum structure of the corresponding nucleus, their wall potential is expected to present some lower threshold windows according to what is predicted by entanglement theory (intrication) and corresponding to Einstein-Rosen bridges [77]. In such conditions, nuclear reactions are then expected to be possible at lower energies, what is not only concerning interstitial

Fig.14. 3d Electron orbital distribution According to calculation of Hydrogen orbital energy levels and distribution by Landau and Lifshitz ref.[77] It shows the complex non isotrope distribution of electronic orbitals corresponding to outer electronic shell of atoms considered for LENR and which can have catalytic properties and/or electronic degenarescence ( for different orbital distribution

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molecules which are corresponding to fusionable nucleus material, but also concerning substitutional atoms which can react with fusionable material belonging to the surrounding lattice (as has been observed with the appearance of new species resulting from transmutation of lattice material [9]. IV.2.2. Duality paradoxe of wave mechanical and elementary particle representation.

Elementary particles of specific mass, electric charge and spin have been assimilated to electromagnetic wave-packets in order to give account for their wave diffraction and interference properties. They have been experimentally observed for instance with electron and neutron diffraction, for which their velocity and mass have been associated to a wave length via the de Broglie formula [78] 1/2mv2 = h.v or λ = h/p with p the impulse = mv Their specific group velocity corresponds to their actual velocity in our spatial reference base and depends on the phase and characteristics of each wave composing the wave-paquet [78]. Collision between those is suggested then corresponding to some dynamic and static interference process between the two corresponding wave-systems. This basic model can give account for production of new wave-paquets with different characteristics according to wave mechanics and corresponding quantum physics fundamentals [76] (including conservation of impulse momentum and energy). However, other particle properties have to be considered such as size, mass and electric charge which used to be defined independently from any wave physics, whenever some attempts have been formulated to associate some mass to the photon energy m* = h.v /c2. They have been determined by the observed corresponding gravity and electromagnetic effects and interactions with which could be formulated some corresponding field theory [76]. They are only considered by their observable effects which can be predicted with the usual electromagnetic and gravity field theory. Several question remains about corresponding currently used fundamentals:

- What is mass, when always associated to kinetic energy and correspond to some quantum cohesion energy with the formula E = mc2

- What is an electric charge from a quantum mechanical point of view when it could never be evidenced independently from mass. Further on when photon is known to have no electric charge and neutral particle with mass exist.

- What is causing the spin ? Rotation of an electromagnetic wave-packet - Why constant velocity of light in vacuum? Independent from relativity

In order to consider some essence of mass, electric charges and electromagnetic waves it can be suggested the existence of a medium (non-viscous elastic fluid corresponding to some absolute quantum vacuum (ether) having specific density of energy. It will be assumed that all sorts of progressing and stationary vibration modes can be sustained or which can decay in being transformed into other wave-paquets without energy losses. Using then analogy with classical wave propagation in homogeneous solids, liquids and gases, light velocity can then be expressed with similar formula: C= √k/ρ° considering

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mass being equivalent to energy (E = mc2) ρ° is then suggested to correspond to the absolute reference quantum vacuum density of cohesion energy, where no elastic wave is modifying the density of cohesion energy.

We suggest postulating then that mass and electric charge of a particle will be defined by some specific characteristics and configuration of corresponding wave-paquet. Especially in considering transversal, longitudinal vibration modes (similar than for phonon waves) and considering in addition their vibration symmetry with which some mean wave paquet energy will be possible to be defined. Taking into account some vacuum ether continuity, a local perturbation of the density of cohesion energy is expected to have long-range effects. Electric, gravity and electromagnetic interactions between wave-paquets is then suggested to be the consequences of some respective spatial distribution of the quantum vacuum perturbation and some principle of lowest action. Juxtaposition of spatial volumic zone of different density of cohesion energy (compression, or depression) is then possible to give account for attraction and repulsion of corresponding wave-packets and considering the isotropy of the quantum vacuum and the conservation of energy, some force fields can be defined which are varying with 1/r2. We provide some schematic representation of corresponding wave-paquet categories with Fig.15

With the wave packet representation of a nucleous, no distinct subparticle can be identified supposed to be sticked to each other by strong force and virtual particles Resulting fission and fusion particles will have each their own wave-packet representation ruled by conservation of energy and impulse, and 3D wave-mechanics.

Fig.15 Schematic representation of mass and electric charge wave-packet

- Wave amplitude distribution depending on group velocity V - Combined longitudinal /transverse waves ~ M+E wave-packet (mass and electric charge) - If no velocity: Ewave orthogonal to Mwave => No mass /charge interaction - Moving Mwave-packet => modification of longitudinal wave mean energy (kinetic energy) - E field by other Ewave-packet => velocity of M+Ewave-packet

* Interaction between Mwave-packets=> gravity * Interaction between Ewave-packets=> electrostatic force

* Interaction between moving Ewave-packets => electromagnetic interaction

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IV.3. Lawson criterion revisited description With the nucleus wave-paquet representation fusion between two nucleuses is to be considered in term of interference between the respective nucleuses wave-systems. Because of the limited volumic size of each wave-paquet (~λ3), the two nucleus wave-paquet can only interfere, if the two wave-paquet can be sufficiently superposed for a time corresponding to their wave period T =1/ν (ν wave frequency). Considering λ the wave length of the smallest wave-paquet (here from H nucleus) and E the energy of this wave packet (E = hν = 1/2mv2 = p2/2m) The density of the wave-paquet should be higher than the density corresponding to the smallest adjacent joining wave-paquet N° = 1/ λ3 = (1/h3).(2m E)3/2 and should be interacting with the other wave-paquet for a time corresponding at least to the shortest period T° with T° = λ.(m/2) ( the same for both wave-paquet Because T=h/E )

Therefore: Nt > N°T° = √ 2E (1/h2).(m)3/2 This reformulated Lawson criterion, show the importance to have lowest colliding energies, what can be interpreted in terms of cross section which is getting smaller with increasing colliding energy. However it must also be associated to the electric barrier potential, which for smaller free nucleus, will stay of same order of magnitude. Whenever not known how this electric barrier potential can be modified in condensed matter, it can be at least be used some published results as a comparative references, which have been achieved for instance for collision between energetic H+ ion beam with a plasma obtained by laser evaporation, for which the density will be at least about 1000 times lower than in a solid state material. Therefore, an optimized compromise is expected to be possibly found, making use on one hand of the higher solid state atomic density, and on other hand the possibility to make use of proton of higher energy, and with the expected possibility to work with some reduced electric barrier potential within condensed matter. IV.4 Application to Condensed Matter Nuclear Fusion Reactor IV.4.1. Condition of energy production with significant COP We have to come back on the problematic of the first attempts to produce LENR fusion energy with help of electrolysis, for which the produced atomic hydrogen ( deuterium will have to be kept adsorbed on the electrode material surface to some extend. It will be expected that some hypothetic fusion will only be possible to be produced, when a sufficient density of adsorbed H (or D) is available. However, this will much depends on the electrode material structure, porosity and surface rugosity, and its eventual catalytic properties with which the atomic H (or D) can at least be in some parts recombined from a chemical point of view, and what can release quite high chemical recombination energy release. It has then to be considered that some random part of the produced atomic hydrogen, will be diffusing into the cathode material, and that not all produced hydrogen atom will be put together. In addition some other part of the released chemical recombination energy might be used for some endothermic atomic rearrangement into a

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different or modified structure. They are then many hazardous aspects which can affect the reproducibility of the released heat, depending wether the electrode material will be too much or not enough porous, and what is the actual material structure of the powder particle, how it has been sintered, what is it contamination etc. Some other type of reactor [10] basing on catalytic effects (the CAT reactor from A.Rossi) has been described having sufficient COP [10] (Coefficient of Performance, in otherword ratio of output energy/input energy). The energy production mechanism has been attributed to LENR since no classical thermodynamic phenomena would have explained the observed energy excess produced. This reactor is making use of a porous Ni rich Ni/Li/Al powder allowing first either water or H2 molecules to be adsorbed in the core of the material and to be then dissociated into atomic hydrogen with the catalytic properties of the Ni material. Considering water vapor as a precursor fuel material, hydrogen will be produced with combined effect of catalysis and AL2O3. At this stage, the released atomic hydrogen can have different use. One part will be used for chemical recombination energy release and the other part will be possibly used for different LENR including HLi fusion and HNi fusion. In order to be able to work continuously, the produced AL2O3 associated to heat can be reduced with the oxidation of Li. However, from time to time, the Li oxide will have to be regenerated with some hot flush of H2. With these first examples, it appears that COP will depend on several main factors: * Precursor fuel material should be produced with sufficient rates and brought on sites where it can produce fusion reaction in sufficient amount.

*The energy consumtion for the achievement of this first condition should be low. *Fusion reaction might be associated to chemical reaction producing energy release. *Eventual atomic rearrangement, which can affect the transport of precursor material,

or the possibility for them to produce LENR. *Regeneration mechanisms in terms of energy consumption and time off.

* Safety and control of power. IV.4.2. Principle of faisible carbon Bethe CNO cycle fusion reactor The Bethe CNO fusion cycle in stars makes use of free atoms and for which H+ is the main precursor material meanwhile the carbon is regenerated at the end of the cycle. The involved nuclear reactions (listed in table 3.) are already produced with relatively low collision energies (~1KeV) and can be significantly enhanced with higher energies up to 5KeV. This range of energy correspond to ion energies which are of quite common use in many surface science equipments and which are low compared to more usual proton-proton and deuterium –deuterium reactions (~ 10KeV to 100KeV). It appears interesting to consider this sort of nuclear reactions in a carbon reactor, when several other attractive arguments can be developped. The cycle is regenerating the carbon, and produces no neutrons and no secondary radioactive waste, whenever emitting some γ. Experimental studies achieved with proton irradiation about 1 to 5 Kev on carbon

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composite material and related materials kept at relatively high temperature (~1500°K) have shown that the H+ are implanted up to 80% of them to depth about 100 nm [79-80] with much reduced erosion rates. With these features, it appears that somewhat energetic collision (1KeV) can be produced with carbon atoms within the bulk of dense carbon materials, at depth about 50 nm where the target carbon is surrounded by a dense atomic network, which might be reducing somewhat the electrostac barrier potential of the nucleus, meanwhile atomic packing density up to thousand times higher than in a plasma is achieved and for which the Lawson condition appears to be quite optimum. Quite intense flux of such H+ irradiation 5~1 mA/cm2 is quite commonly achieved with equipment similar to those used or different technologic coating. Recombined H2 is contributing to increase the hardness and the density of the carbon material, and will prevent the coating to be degraded by the heat release all the more UV irradiation can help to maintain the desired more dense carbon quality. The carbon can be easily regenerated, and the H+ irradiation intensity can be easily controlled with appropriate pulsed modes. Secondary reaction with helium, nitrogen and oxygen, will contribute to the energy production efficiency. V.CONCLUSIONS With this presentation we have shown how quantum electronic sp3 atomic rearrangement can be observed in carbon materials in making use of revisited Raman spectroscopy fundamentals and how different kind of atomic rearrangement can be produced and under which conditions. We have shown that this sort of atomic rearrangement activation is mainly produced by chemical energy energy release of H2 N2 and C-C adsorbtion energy release and how it is applicable to many other materials including metals for which the atoms present different chemical states. We have furthermore shown how the Lawson criterion, with which the nuclar fusion conditions can be adapted to ion/ condensed matter interaction. This could be achieved after having revisited almost qualitatively some aspect of nuclear quantum mechanic. We have considered here some properties of a quantum vacuum where 3D density of cohesion energy wave-paquet will interact similarly to classical wave mechanic in non viscous fluids and where the wave-paquets will be considered as the elementary particles themselves including all their properties and energy states. We could then show how atomic rearrangement and their associated specific different thermodynamics can affect the evaluation of some gas absorption and the measurement of different energy release. We finally have proposed some principle of carbon proton fusion reactor basing on the CBO Bethe cycle, where proton interact with nucleus belonging to a dense condensed carbon matter and for which best COP can be expected. This is to be considered with the point that the carbon target material can be easily kept in its stable dense structure making use of the sp3 quantum electronic atomic rearrangement , and in that the considered reactions can be produced with relatively reduced H+ energies.

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References 1) T.J. Carter, L.A. Cornish Engineering Failure Analysis, Vol. 8, N°2, (2001) 113–121 2) S.Neuville and A.Matthews, Thin Solid Films Vol 515 (2007) 6619 3) O.J.A.Schueller, S.T.Brittain, C.Marzollin, G.M.Whitesiders, Chem.Mater.9 (1997) 1399 4) Y.Lin, L.Zhang, H.K.Mao, P.Chow, Y.Xiao, M.Baldini, J.Shu and W.Mao, Physical Review Letters 107 (2011) 175504 5) S.Neuville, New Application Perspective for Tetrahedral Amorphous Carbon Coatings QScience Connect 2014:8 http://dx.doi.org/10.5339/connect.2014.8 6) S.Neuville Surf.Coat.Technol, Vol206 N°4(2011)703 7) R.W.Cahn and P.Haasen Editors Physical Metallurgy (Fourth Edition) ISBN: 978-0-444-89875-3ELSEVIER (1996) 8) D.F.Shriver, P.W.Atkins, C.H.Langford, Inor.Chem.Oxford University Press, New York (1989) 337 9) P.Roca I Cabarrocas, N.Layadi J.of Vac.Sci.Technol. A16 (2)(1998)436. 10) M.C.H. McKubre, Cold Fusion (LENR). “One Perspective on the State of the Science” in 15thInternational Conference on Condensed Matter Nuclear Science. 2009. Rome, Italy: ENEA 11) J.D.Lawson (December 1955). “Some Criteria for a power producing thermo-nuclear reactor”. (Technical report). Atomic Energy Research Establishment, Harwell, Berkshire, U. K. A.E.R.E. GP/R 1807 12) K.S.Krane, "Introductory Nuclear Physics"(Bethe CNO cycle) John Wiley & Sons, New York (1988) 537

Table 3. Bethe CNO fusion cycle 12C + 1H → 13N + γ +1,95 MeV 13N → 13C + e+ + νe +2,22 MeV 13C + 1H → 14N + γ +7,54 MeV 14N+ 1H → 15O + γ +7,35 MeV 15O → 15N + e+ + νe +2,75 MeV 15N + 1H → 12C + 4He +4,96 MeV

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13) J.L.Bredas, G.B.Street, EMRS Meeting XVII, Proceedings by P.Koidl and P.Oelhafen, Les Editions de la Physique (Eds) (1987) 237 14) S.Neuville, “Carbon Structure Analysis with differentiated Raman Spectroscopy” (2014) Lambert Academic Publishing (Saarbrücken Germany) ISDN 978-3-659-48909-9. 15) D.G.Liu, J.P.Tu, C.F.Hong, C.D.Gu, and S.X.Mao, Surf. Coat.Technol. 205 (2010) 152 16) A.P.Badzian, P.K.Bachmann, T.Hartnett, T.Badzian and R.Messier, EMR Meeting XVII, Proceedings by P.Koidl and P.Oelhafen, Les Editions de la Physique (Eds) (1987) 63. 17) F.Tuinstra, J.L.Koenig, J.Phys.Chem.53 (1979) 1126 18) M.S.Dresselhaus, G.Dresselhaus, R.Saito, AJorio, Physics Reports 409(2005) 47-99 19) S.Anders, J.W.AgerIII, G.M.Pharr, T.Y.Tsui, I.G.Brown, Thin Solid Films 308309(1997) 186 20) J.Robertson, Diamond and Related Materials 3 (1994) 732 21) A.C.Ferrari, Diamond and Related Materials 11 (2002) 440 23) K.E.Spear, A.W.Phelps, W.B.White, J.Mater.Res.5 (1990) 2277 24) B.Marcus, L.Fayette, M.Mermoux, L.Abello, and G.Lucazeau, J.App.Phys.Vol4 (1994)3463 25) L.Fayette, B.Marcus, M.Mermoux, G.Tourillon, K.Laffon, P.Parent, and F.Le Normand, Phys. Rev. B Vol 57 N°22 (1998) 1412 26) B.Dischler, EMRS Meeting XVII, Proceedings by P.Koidl and P.Oelhafen, Les Editions de la Physique (Eds) (1987) 189 27) P.V.Huong, B.Marcus, M.Mermoux, D.K.Veirs, G.Rozenblatt, Diamond and Related Materials I (1992) 869 28) K.M.McNamara, KK.Gleason, G.J.Vestyck, J.E.Butler, Diamond and Related Materials 1 (1992) 1145 29) J.Campos-Delgado, Y.A.Kim, T.Hayashi, A.MorelosGomez, M.Hofmann, M.Endo, H.Muramatsu, H.Terrones, R.D.Shull, M.S.Dresselhaus, M.Terrones. Chem.Phys.Lett.469 (2009)177182 30) L.M.Malard, M.A.Pimenta, G.Dresselhaus, M.S.Dresselhaus, Physics Reports 473 (2009) 5187 31) J.Wagner, M.Ramsteiner, C.Wild, P.Koidl, EMRS Meeting XVII, Proceedings by P.Koidl and P.Oelhafen, Les Editions de la Physique (Eds)(1987) 351 32) S.Prawer, F.Ninio, I.Blanchonette, J.App.Phys. 68 (1990) 2361 33) J.Rouzaud, A.Oberlin, C.BenyBassez, Thin Solid Films 105 (1983) 34) Y.Y.Lin, H.W.Wei, K.C.Leou, H.Lin, C.H.Tung, M.T.Wei, C.Lin, 35) M.Iwaki, K.Takahashi, A.Sekiguchi, J.Mat.Res.5 (1990) 2562. 36) R.Singh, C.V.Raman and the discovery of the Raman Effect, Physics in Perspective (PIP) 4 (4) (2002) 39420 37) R. Rammamurti, V. Shanov, R.N. Singh, S. Mamedov, P. Boolchand, J. Vac. Sci.Technol. A24 (2) (2006) 179.

27

[Texte]

38) M.Lazzeri, C.Attaccalite, L.Wirtz, F.Mauri, Phys. Rev B 7 (2008) 081406 39) R.Zallen. The Physics of Amorphous Solids, Wiley, New York (1983) 40) J.Maultzsch, S.Reich, C.Thomsen, Phys.Rev. B 70 (2004) 155403 41) Y.Pauleau, in C.Donnet and A.Erdemir, Tribology of DLC, Springer, New York (2008) 102 42) J.Robertson and E.P.O’Really, Phys.Rev. B 35 (1987) 2946 43) T.E.J.Dallas, thesis on Structural Phases of Disordered Carbon Materials, Texas Tech University (1996) 44) C.Casiraghi, F.Piazza, A.C.Ferrari, D.Grambole, and J.Robertson, Diamond and Related Materials 14 (2005) 1098 39 45) R.Saito, A.Jorio, A.G.Souza Filho, G.Dresselhaus, M.S.Dresselhaus, M.A.Pimenta, Phys.Rev.Lett. 88 (2002) 027401 46) Y.M You, Z.H.Ni, T.Yu, Z.X.Shen, App.Phys.Lett 93 (2008)163112 47) Y.N.Xu, D.Zhan, L.Liu, H.Suo, Z.H.Ni, T.T.Nguyen, C.Zhao, Z.X.Shen, ACSNano Vol. 5 N°1 (2011) 142 48) R.E.Prange and S.M.Girvin, “The Quantum Hall Effect” (Springer, New York, 1987). 49) A.Mahmood, P.Mallet and J.Y.Veuillen, Nanotechnology 23, (2012) 055706 40) B.Fakrach, A.Rahmani, H.Chadli, K.Sbai, J.L.Sauvajol, Physica E 41 (2009) 1800 51) K.A.Ritter, J.W.Lyding, The Influence of Edge Structure on the Electronic Properties of Graphene Quantum Dots and Nanoribbons, Nat.Mater.(8)(2009) 235242 52) U.Ritter, P.Scharff, C.Siegmung, O.P.Dimmytrenko, N.P.Kulisch, Y.I.Priylutskyy, N.M.Belyi, V.A.Gubanov, S.V.Lizunova, V.G.Poroshin, V.V.Shlapatskaya, H.Bernas, Carbon 44(2006) 2694 53) L.G.Cançado, M.A.Pimenta, B.R.Neves, M.S.Dantas, A.Jorio, Phys.Rev.Lett. 93 (2004) 247401 54) L.G.Cançado, M.A.Pimenta, B.R.Neves, G.MedeirosRibeiro, T.Enoki, Y.Kobayashi, K.Takai M.S.Dantas, K.Fukui, M.S.Dresselhaus, R.Saito, A.Jorio, Phys.Rev.Lett. 93 (2004) 047403 55) M.S.Dresselhaus, A.Jorio, A.G.SouzaFilho, R.Saito, Phil.Trans.R.Soc.A Vol (368) (2010) 53555377. 56) P.K.Bachmann, W.vanEckervort, Diamond and Related Materials 1 (1992) 1021 57) M.Endo, Grow Carbon fibers in the vapor phase, Chemtech (September 1988) 568576 58) G.Flamant, R.Guillard, D.Laplaz, Le Vide N°300 Vol.2-4(2001)266 59) S.Weissmantel, G.Reisse, D.Rost, Surf.Coat.Technol. 188-189 (2004) 268. 60) A. Ohl and J. Röpke, Diamond and Related Materials 1 (1992) 243 61) R.McKenzie, D.Muller, B.A.Pailthorpe, Z.H.Wang, E.Kratchinskaia, D.Segal, P.B.Lukins, P.D.Swift, P.J.Martin, G.Amaratunga, P.H.Gaskel and

28

[Texte]

A.Saeed, DRM Vol1 N°1 (1991) 51 62) B.K.Tay, X.Shi, L.K.Cheah, D.I.Flynn Thin Solid Films 308309 (1997)199 63) J.Eck, J.L.Sans, M.Balat-Pichelin, ECS Transaction 25 (25) (2010)111-121 64) A.P.Badzian, P.K.Bachmann, T.Hartnett, T.Badzian and R.Messier, EMR Meeting XVII, Proceedings by P.Koidl and P.Oelhafen, Les Editions de la Physique (Eds) (1987) 63. 65) K.S.Sankara-Reddy and M.Satyam. Structural ordering of diamond-like carbon films by applied electric field. Solid State Communications, 93 (10) (1995) 797799 66) D.Rai, H.Joshi, A.D.Kulkarni, S.P.Gejji and R.K.Pathak. Electric Field Effects on Aromatic and Aliphatic Hydrocarbons. J. Phys. Chem.AVol.111N°37 (2007) 9111–9121 67) S. Neuville, SNB 121 (2) (2007) 436. 68) C.E. Borroni-Bird, D.A. King, Rev. Sci. Instrum. 62 (9) (1991) 2177. 69) D. Beeman, J. Silvermann, R. Lynds, M.R. Anderson, Phys. Rev. B30 (1984) 870. 70) X.H. Wang, G.H.M. Ma, W. Zhu, J.T. Glass, L. Bergman, K.F. Turner, R.J. Nemanich, Diamond Relat. Mater. 1 (1992) 828. 71) S.Neuville, A.Taggliaferro, Y.Bounouh, S.Vallon, R.Etemadi, J.Perrin, CIP 95 Antibes, Le Vide, Sciences, Techniques et Applications, Vol. 275 (1995) 64 by SFV (Eds), Paris (France). 72) 76) S.Sönderby, A.N.Berthelsen, K.P.Almtoft, B.H.Christensen, L.P.Nielsen, J.Böttiger, Diamond and Related Materials Vol.20, N°56 (2011) 682 73) K.V.Ravi, C.A.Koch, H.S.Hu, A.Joshi, J.Mat.Res. Vol.5 N°11 (1990) 2356. 74) R.Hernberg, T.Lepistö, T.Mäntyla, T.Stenberg, J.Vattulainen, Diamond and Related Materials I (1992) 255 75) L.Eyges, "Physics of the Mössbauer Effect". American Journal of Physics 33 (10) (1965) 790–802 76) L.Landau and E.Lifchitz, Physique Theorique. Coll.MIR.Ellipses Eds.1997 77) A.Einstein, N.Rosen (1935). "The Particle Problem in the General Theory of Relativity". Physical Review 48(1935) 73. 78) Broglie, Louis de. The wave nature of the electron, Nobel Lecture, December 12, (1929). 79) J. Eck, M. Balat-Pichelin, Vacuum Vol 85, N°3, 24 (2010) 380–389 80) M. Balat-Pichelin, J. Eck, S. Heurtault, H. Glénat,Vol 314, (2014) 415–425 ,